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中国精品科技期刊2020

超高效液相色谱-串联质谱法检测卤肉中4种β-受体激动剂残留

孟春杨, 吴玉田, 彭蕾, 钟雪, 邹璐, 刘文政, 周贻兵

孟春杨,吴玉田,彭蕾,等. 超高效液相色谱-串联质谱法检测卤肉中4种β-受体激动剂残留[J]. 食品工业科技,2024,45(1):277−283. doi: 10.13386/j.issn1002-0306.2023030044.
引用本文: 孟春杨,吴玉田,彭蕾,等. 超高效液相色谱-串联质谱法检测卤肉中4种β-受体激动剂残留[J]. 食品工业科技,2024,45(1):277−283. doi: 10.13386/j.issn1002-0306.2023030044.
MENG Chunyang, WU Yutian, PENG Lei, et al. Determination of 4 Kinds of β-Agonists Residues in Braised Meat by Ultra Performance Liquid Chromatography-Tandem Mass Spectrometry[J]. Science and Technology of Food Industry, 2024, 45(1): 277−283. (in Chinese with English abstract). doi: 10.13386/j.issn1002-0306.2023030044.
Citation: MENG Chunyang, WU Yutian, PENG Lei, et al. Determination of 4 Kinds of β-Agonists Residues in Braised Meat by Ultra Performance Liquid Chromatography-Tandem Mass Spectrometry[J]. Science and Technology of Food Industry, 2024, 45(1): 277−283. (in Chinese with English abstract). doi: 10.13386/j.issn1002-0306.2023030044.

超高效液相色谱-串联质谱法检测卤肉中4种β-受体激动剂残留

基金项目: 贵州省卫生健康委科学技术基金项目(gzwkj2022-268);贵州省科学(青年)技术基金项目(2021-E1-2青)。
详细信息
    作者简介:

    孟春杨(1987−),女,硕士,主管技师,研究方向:食品风险监测,E-mail:yang554677318@163.com

    通讯作者:

    吴玉田(1992−),男,硕士,主管技师,研究方向:理化检验,E-mail:wuyt0501@163.com

  • 中图分类号: O657.63

Determination of 4 Kinds of β-Agonists Residues in Braised Meat by Ultra Performance Liquid Chromatography-Tandem Mass Spectrometry

  • 摘要: 建立了一种超高效液相色谱串联质谱(ultra-high performance liquid chromatography-tandem mass spectrometry,UPLC-MS)检测卤肉中4种β-受体激动剂(特布他林、克仑特罗、莱克多巴胺、沙丁胺醇)的方法。样品经β-盐酸葡萄糖醛酸苷酶/芳基硫酸酯酶解后,经SLS固相萃取柱净化。以0.1%甲酸水和乙腈为流动相梯度洗脱,用Thermo Hypersil Gold C18色谱柱分离,ESI+进行多反应监测(MRM),内标法定量。4种β-受体激动剂在浓度为0.5~9.5 μg/L范围内线性关系良好,相关系数(r)均大于0.9988,检出限(LOD)为0.1 μg/kg,定量限(LOQ)为0.3 μg/kg。3个加标水平下(1、5、9 μg/kg)的回收率在87.9%~113.7%之间,RSD为1.48%~9.32%。162批次卤肉样品,有一份卤猪蹄样品检出克伦特罗含量为1.51 μg/kg,莱克多巴胺为3.65 μg/kg;另外一份卤羊肉样品检出克伦特罗含量11.5 μg/kg。本方法快速准确,可用于卤肉中4种β-受体激动剂(特布他林、克仑特罗、莱克多巴胺、沙丁胺醇)的定性、定量检测。
    Abstract: An ultra-high performance liquid chromatography-tandem mass spectrometry (UPLC-MS) method was developed for the determination of four β-agonists (terbutaline, clenbuterol, ractopamine, salbutamol) in braised meat. Samples were hydrolyzed by β-glucuronidase and cleaned up by an SLS solid phase extraction column. The separation was performed on a Thermo Hypersil Gold C18 column with a gradient elution of 0.1% formic acid water and acetonitrile as mobile phases, ESI+ was used for multiple response monitoring (MRM) and quantitative analysis by internal standard method. The linear relationship of the four β-agonists was good in the concentration range of 0.5 μg/L to 9.5 μg/L, and the correlation coefficient (r) was greater than 0.9988. The limit of detection (LOD) was 0.1 μg/kg, and the limit of quantitation (LOQ) was 0.3 μg/kg. The recoveries were 87.9%~113.7% and RSDs were 1.48%~9.32% at three spiked levels (1, 5 and 9 μg/kg). In a total of 162 batches of braised meat samples, one sample of braised pig’s trotter was found to contain 1.51 μg/kg of clenbuterol and 3.65 μg/kg of ractopamine. Additionally, another sample of braised lamb was found to contain 11.5 μg/kg of clenbuterol. The method is rapid and accurate, and can be used for qualitative and quantitative determination of four β-agonists (terbutaline, clenbuterol, ractopamine, salbutamol) in braised meat.
  • β-受体激动剂又称瘦肉精,是苯乙醇胺类化合物,该类药物可明显提高动物的瘦肉率,因此会被非法添加于畜禽类饲料中[13]。当人体食入含有β-受体激动剂的动物组织将会出现心悸、 恶心、肌肉震颤和紧张等症状[46]。我国已禁止在畜禽类养殖中使用β-受体激动剂[7],但在利益的驱使下,还是存在β-受体激动剂非法添加的情况[810]

    目前对于β-受体激动剂的检测方法,常用酶联免疫法[1112]、气相色谱-串联质谱法[1315]和液相色谱-串联质谱法[1618]等。酶联免疫法假阳性率较高,气相色谱-质谱法需要进行衍生后测定,操作过程复杂,且检测灵敏度低,不适用于多种目标物同时分析[1921]。相较于其他的检测技术,液相色谱-串联质谱法具有灵敏度高、选择性强、分析速度快和样品使用量少等优点,已经广泛应用于食品污染物监测[10,2223]。市场监管部门对肉制品的监督检测主要是新鲜肉,一些在饲养中有非法添加的肉就存在制成卤肉售卖的风险。卤料成分极其复杂,因此卤肉基质效应大,容易受到干扰出现假阳性。目前动物源性食品中β-受体激动剂的国标检测方法(GB 31658.22-2022)[24]实验前处理操作过程繁琐,提取的样品溶液非缓冲盐体系,需要两次调节pH,两次氮吹复溶,操作繁琐耗时,不适合大批量样品的检测。近几年文献报道的QuEChERS EMR-Lipid净化快速检测肉制品中β-受体激动剂的方法[2527],操作简单,但主要是除去样品中的脂肪,无法完全去除卤肉中的杂质,检测卤肉易出现假阳性。

    为最大限度地消除基质干扰,本实验采用基质标准曲线,同时采用同位素内标矫正。采用基质标准曲线可使样品溶液和标准溶液有相同的离子化环境,从而减小基质效应[2526,28],采用与待测化合物相对应的同位素内标校正,同位素内标稀释技术提高了β-受体激动剂定量分析的准确性和回收率,消除基质的干扰[27,2930]。本文在国标方法GB31658.22-2022的基础上,简化了萃取步骤,且仅需调节pH一次,氮吹复溶一次,建立了将卤肉样品用乙酸钠-醋酸缓冲液提取,仍采用经典的SLS固相萃取柱净化,UPLC-MS测定卤肉中4种β-受体激动剂的方法,为卤肉中β-受体激动剂的检测提供了新的思路。

    甲醇、乙腈 色谱纯,Thermo公司;甲酸 色谱纯,中国阿拉丁公司;浓氨水 优级纯,沪试公司;乙酸乙酯、盐酸、乙酸钠、醋酸 均为分析纯,均为国药集团化学试剂有限公司;β-葡萄糖醛苷酸酶/芳基硫酸酯酶 硫酸酯酶活性<20000 units/mL,美国CNW;特布他林、克仑特罗、莱克多巴胺、沙丁胺醇、D9-特布他林、D9-克仑特罗、D5-莱克多巴胺、D3-沙丁胺醇 均为TRC加拿大公司,纯度均大于95%;卤肉:卤羊肉、卤牛肉、卤猪肉等 来自于贵州省的九个市州。

    SLS固相萃取柱 (500 mg/6 mL) 福州勤鹏生物科技有限公司;QuEChERS dSPE EMR-Lipid、QuEChERS Final Polish  美国安捷伦科技有限公司;Oasis MCX固相萃取柱(500 mg/6 mL)、Oasis HLB固相萃取柱(200 mg/6 mL) Waters公司;Millipore A10超纯水机 美国密理博公司;SCIEX 6500三重四极杆串联质谱仪 美国AB SCIEX公司;3-30KS离心机 德国Sigma公司;DMV-16涡旋混匀仪 广东科寅设备有限公司;N-EVAP氮吹仪 上海安普科技有限公司;SHA-C水浴恒温振荡器 金坛市恒丰仪器厂;F2 pH计 梅特勒-托利多仪器上海有限公司。

    分别准确称取0.010 g的特布他林、克仑特罗、莱克多巴胺、沙丁胺醇的标准品于4个10 mL容量瓶中,用甲醇溶解并定容至刻度,摇匀,得到1000 mg/L的各单标储备液。取各单标储备液各0.1 mL于10 mL容量瓶中,用甲醇溶解并定容至刻度,摇匀,得到10 mg/L的混合标准储备溶液。临用前逐级稀释成10 μg/L的混合标准使用液。

    分别准确称取0.010 g的D9-特布他林、D9-克仑特罗、D5-莱克多巴胺、D3-沙丁胺醇标准品于4个10 mL容量瓶中,用甲醇溶解并定容至刻度,摇匀,得到1000 mg/L的各同位素内标储备液。取各同位素内标储备液各0.1 mL于10 mL容量瓶中,用甲醇溶解并定容至刻度,摇匀,得到10 mg/L的混合同位素内标储备溶液。临用前逐级稀释成100 μg/L的混合同位素内标使用液。

    称取绞碎卤肉2.00 g样品于50 mL 离心管中,加100 μL 100 μg/L β-受体激动剂混合同位素内标使用液静置10 min,加10 mL 0.2 mol/L pH5.2的乙酸钠-醋酸缓冲液,均质20 s,加入20 μL β-葡萄糖醛苷酶/芳基硫酸酯酶液,37 ℃水浴振荡器水解16 h,取出冷却,10000 r/min 离心10 min,取上清液,用3.0 mol/L盐酸溶液调节pH至2.0±0.1(pH测定仪),10000 r/min 离心10 min,上清液待净化。

    SLS固相萃取柱依次用5 mL水、5 mL甲醇、5 mL水、5 mL 40 mmol/L的盐酸溶液活化后,取5 mL上述样品上清液至柱内过柱,然后用5 mL水、5 mL甲醇依次淋洗除杂,抽干,用10 mL 5%氨化乙酸乙酯洗脱,收集洗脱液于10 mL聚丙烯离心管中,50 ℃水浴中氮吹干。初始流动相复溶,涡旋混匀,0 ℃ 7000 r/min离心5 min,上清液进UPLC-MS测定。

    色谱柱:Thermo Hypersil Gold C18 (100 mm×2.1 mm,1.9 μm);柱温:35 ℃;进样量:5 μL;流速0.3 mL/min;流动相A为0.1%甲酸-水;流动相B为乙腈;梯度洗脱条件:0~0.5 min 95%A,0.5~8.0 min 95%的A线性变化为40%,8.0~9.0 min 40%A,9.1~13.0 min 95%A。

    离子源:ESI+;离子化电压:4500 V;气帘气压强:35 psi;喷雾气压强:50 psi;辅助加热气压强:50 psi;碰撞气:Medium。多反应监测(MRM)模式进行采集。

    UPLC-MS配有SCIEX OS数据处理软件建立标准曲线、计算结果,采用Microsoft Excel处理数据及绘制图表。谱图为Photoshop作图软件绘制。本文净化柱的选择和回收率均采用6个平行样品计算。

    在电喷雾离子源正离子模式下,流动相中加入适量甲酸可增强待测组分离子化效率,提高检测响应强度,且乙腈比甲醇有更强的洗脱能力,因此选择乙腈-0.1%甲酸水作为流动相,4种β-受体激动剂的色谱峰形和响应信号的强度也较好。调整洗脱程序,使各组分分离,优化后的色谱条件见1.2.3.1,优化后的谱图如图1所示。

    图  1  4种 β-受体激动剂的离子流色谱图
    Figure  1.  Ion chromatograms of 4 kinds of β-agonists

    选择ESI+模式对目标物进行质谱扫描。将质量浓度为50 μg/L的各标准液进入质谱,通过Q1扫描找到各目标物的母离子,再对母离子施加一定的碰撞能量进行Product Ion(MS2)扫描,获得各自的二级碎片离子,选择2个信号较强且干扰小的碎片离子与其母离子组成监测离子对。优化碰撞能量、锥孔电压等各项质谱参数,建立MRM的检测模式。最终确定的离子对信息及质谱参数如表1所示。

    表  1  质谱参数
    Table  1.  Mass spectrometric parameters
    化合物名称 母离子(m/z) 子离子(m/z) 碰撞能量(eV) 去簇电压(V) 扫描时间(ms)
    克仑特罗 277.1 203.1* 23 32 100
    259.2 16 31 100
    D9-克仑特罗 286.2 204.1 23 91 100
    特布他林 226.2 152.3* 23 31 100
    125.1 34 27 100
    D9-特布他林 235.2 153.2 23 85 100
    莱克多巴胺 302.2 164.3* 23 37 100
    284.4 17 37 100
    D5-莱克多巴胺 307.2 165.3 23 52 100
    沙丁胺醇 240.1 148.2* 26 35 100
    222.1 15 34 100
    D3-沙丁胺醇 243.2 151.1 27 53 100
    注:*为定量离子。
    下载: 导出CSV 
    | 显示表格

    本课题组李磊等[31]已确证QuEChERS EMR-Lipid净化HPLC-MS测定猪肉猪肝中β-受体激动剂简便可行,在实验中发现此净化方法测定卤肉中β-受体激动剂,高检出率和同一样品同时检出多种β-受体激动剂,数据可疑,可能出现假阳性。如图2所示,同一卤肉样品经SLS柱净化后上机为a图,克伦特罗和莱克多巴胺均未检出。QuEChERS EMR-Lipid净化后上机如b图,在5.28 min处出峰,说明莱克多巴胺有检出;在5.74 min处出峰,说明克伦特罗有检出。采用国标法对这一卤肉样品进行净化复检,克伦特罗和莱克多巴胺均未检出。结果证实QuEChERS EMR-Lipid净化虽然快速简便,但清除不干净卤肉样品中杂质,容易导致假阳性结果,不适合卤肉样品的净化。QuEChERS EMR-Lipid是一种分散固相萃取技术,原理是特殊聚合物基质EMR专门吸附脂质中C5及以上的碳链,对脂质具有非常强的选择吸附性,主要用途是在前处理过程中去除食品基质中的脂质。而经典的SLS柱是利用选择性吸附与选择性洗脱的液相色谱法分离原理,是使液体样品溶液通过吸附剂,保留其中被测物质,再选用适当强度溶剂冲去杂质,然后用少量溶剂迅速洗脱被测物质,从而能更加完全地清除杂质,更适用于复杂基质。

    图  2  SLS柱净化上机(a)和QuEChERS EMR-Lipid净化上机(b)的MRM离子提取色谱图
    Figure  2.  MRM extracted ion chromatograms of SLS column purification (a) and QuEChERS EMR-Lipid purification (b)

    为了使目标化合物的定量分析更加准确,采用的净化柱要能够降低或消除样品基质带来的干扰。肉类中β-受体激动剂的前处理多采用PXC柱、HLB柱、SLS柱、MCX柱、QuEChERS EMR-Lipid等净化,本研究排除了QuEChERS EMR-Lipid,又对比了SLS柱、HLB柱和MCX柱净化的效果。对加标量5.0 μg/kg空白卤牛肉的净化效率,平行测定6次,对比其平均回收率,RSD在1.23%~7.92%之间,结果见图3

    图  3  不同类型净化柱的回收率
    Figure  3.  Average recovery of different purification columns

    结果显示:HLB柱净化,4种β-受体激动剂的回收率都不高,这是因为HLB柱是共价键结合分配原理,不适用于β-受体激动剂这类中等强极性化合物[32]。SLS柱和MCX柱净化均为强阳离子交换柱,但SLS柱的回收率为89.2%~97.9%优于MCX柱的83.2%~90.4%(详细结果见图3),因此选择SLS柱作为净化柱。

    取适量的10 μg/L的混合标准使用液和100 μg/L的混合同位素内标使用液,用空白基质溶液配制成含混合内标5 μg/L的0.5、1.0、2.0、4.0、6.0、8.0、9.5 μg/L基质匹配标准系列溶液。以系列标准溶液中分析物的浓度(μg/L)与对应的同位素内标的峰面积比值绘制校正曲线,按内标法计算试样中β-受体激动剂含量。以3倍信噪比计算方法的检出限(3S/N),以10倍信噪比计算方法的定量限(10S/N),结果见表2

    表  2  β-激动剂线性方程、检出限和定量限
    Table  2.  Linear equation, detection limit and quantitation limit of β-agonists
    化合物 线性回归方程 相关系数 检出限
    (μg/kg)
    定量限
    (μg/kg)
    克仑特罗 y=0.20865x−0.00440 0.99918 0.1 0.3
    特布他林 y=0.29622x+0.02664 0.99953 0.1 0.3
    莱克多巴胺 y=0.36347x−0.01383 0.99948 0.1 0.3
    沙丁胺醇 y=0.21278x−0.01485 0.99882 0.1 0.3
    下载: 导出CSV 
    | 显示表格

    表2可知4种β-受体激动剂在0.5~9.5 μg/L浓度范围内r值>0.9988,计算特布他林、克仑特罗、莱克多巴胺、沙丁胺醇的检出限均为0.1 μg/kg,定量限为0.3 μg/kg。与部分已有方法[21,29]相比检出限和定量限更低,定量更为精准可靠。

    在2.0 g空白卤肉样品中加入1、5、9 μg/kg的3个不同浓度水平的4种β-受体激动剂标准溶液,同时加入含有和标准曲线相同浓度的内标溶液,每个浓度水平平行测定6次,计算回收率及测定值的相对标准偏差(RSD),结果见表3

    表  3  β-激动剂回收率与精密度结果
    Table  3.  Spiked recoveries and RSDs of β-agonists
    化合物加标浓度(μg/g)测定值(μg/g)回收率(%)RSD(%)
    克仑特罗1.000.9090.28.47
    5.004.8496.91.48
    9.008.9999.92.33
    特布他林1.000.9090.39.32
    5.005.69113.78.85
    9.009.43104.84.00
    莱克多巴胺1.000.9393.37.50
    5.004.3987.96.54
    9.008.1290.27.89
    沙丁胺醇1.000.9998.79.02
    5.004.6993.95.85
    9.008.4493.84.85
    下载: 导出CSV 
    | 显示表格

    表3可知,4种β-受体激动剂的回收率在87.9%~113.7%之间,RSD在1.48%~9.32%之间,表明方法回收率和精密度良好。

    从贵州省的九个市州每个市(州)采集18份样本,其中18份样本要求区域内的每个县(区)至少采集2份,所有采集的样本均为当地集市随机抽取。用SLS固相萃取柱净化,超高效液相色谱-串联质谱法对采集的162批次卤肉试样(有卤羊肉,卤牛肉,卤猪肉等)中的4种β-受体激动剂进行检测,结果有2份阳性样品。其中采自遵义市农贸市场的一份卤猪蹄样品克伦特罗含量为1.51±0.16 μg/kg,莱克多巴胺为3.65±0.28 μg/kg;另外一份采自遵义市农贸市场的卤羊肉样品克伦特罗含量为11.5±0.29 μg/kg。用国标方法对阳性样本进行复检,卤猪蹄样品克伦特罗含量为1.56±0.07 μg/kg,莱克多巴胺为3.51±0.15 μg/kg;卤羊肉样品克伦特罗含量为11.7±0.20 μg/kg。食品中兽药最大残留限量标准GB 31650-2019和食品中41种兽药最大残留限量GB 31650.1-2022中克伦特罗、特布他林、莱克多巴胺、沙丁胺醇都是禁用药物,而本实验在卤肉中检出,已有食品风险安全隐患,相关部门应引起重视。

    本研究建立了SLS固相萃取柱净化,超高效液相色谱-串联质谱法检测卤肉中克伦特罗、特布他林、莱克多巴胺、沙丁胺醇4种β-受体激动剂残留的方法,并对仪器条件以及前处理方法进行了优化。该方法能有效地除去基质干扰,检出限为0.1 μg/kg,定量限为0.3 μg/kg,加标回收率在87.9%~113.7%之间,相对标准偏差1.48%~9.32%。该方法方便快速、准确可靠,满足实际样品检测要求,可为卤肉中β-受体激动剂类化合物兽药残留的监测提供技术支撑,有助于卤肉中β-受体激动剂类化合物兽药残留的市场监管。

  • 图  1   4种 β-受体激动剂的离子流色谱图

    Figure  1.   Ion chromatograms of 4 kinds of β-agonists

    图  2   SLS柱净化上机(a)和QuEChERS EMR-Lipid净化上机(b)的MRM离子提取色谱图

    Figure  2.   MRM extracted ion chromatograms of SLS column purification (a) and QuEChERS EMR-Lipid purification (b)

    图  3   不同类型净化柱的回收率

    Figure  3.   Average recovery of different purification columns

    表  1   质谱参数

    Table  1   Mass spectrometric parameters

    化合物名称 母离子(m/z) 子离子(m/z) 碰撞能量(eV) 去簇电压(V) 扫描时间(ms)
    克仑特罗 277.1 203.1* 23 32 100
    259.2 16 31 100
    D9-克仑特罗 286.2 204.1 23 91 100
    特布他林 226.2 152.3* 23 31 100
    125.1 34 27 100
    D9-特布他林 235.2 153.2 23 85 100
    莱克多巴胺 302.2 164.3* 23 37 100
    284.4 17 37 100
    D5-莱克多巴胺 307.2 165.3 23 52 100
    沙丁胺醇 240.1 148.2* 26 35 100
    222.1 15 34 100
    D3-沙丁胺醇 243.2 151.1 27 53 100
    注:*为定量离子。
    下载: 导出CSV

    表  2   β-激动剂线性方程、检出限和定量限

    Table  2   Linear equation, detection limit and quantitation limit of β-agonists

    化合物 线性回归方程 相关系数 检出限
    (μg/kg)
    定量限
    (μg/kg)
    克仑特罗 y=0.20865x−0.00440 0.99918 0.1 0.3
    特布他林 y=0.29622x+0.02664 0.99953 0.1 0.3
    莱克多巴胺 y=0.36347x−0.01383 0.99948 0.1 0.3
    沙丁胺醇 y=0.21278x−0.01485 0.99882 0.1 0.3
    下载: 导出CSV

    表  3   β-激动剂回收率与精密度结果

    Table  3   Spiked recoveries and RSDs of β-agonists

    化合物加标浓度(μg/g)测定值(μg/g)回收率(%)RSD(%)
    克仑特罗1.000.9090.28.47
    5.004.8496.91.48
    9.008.9999.92.33
    特布他林1.000.9090.39.32
    5.005.69113.78.85
    9.009.43104.84.00
    莱克多巴胺1.000.9393.37.50
    5.004.3987.96.54
    9.008.1290.27.89
    沙丁胺醇1.000.9998.79.02
    5.004.6993.95.85
    9.008.4493.84.85
    下载: 导出CSV
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  • 收稿日期:  2023-03-02
  • 网络出版日期:  2023-11-02
  • 刊出日期:  2023-12-31

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